CN1251989C - Novel vacuum degassing method for gelcasting ceramic slurry - Google Patents
Novel vacuum degassing method for gelcasting ceramic slurry Download PDFInfo
- Publication number
- CN1251989C CN1251989C CN 200410039112 CN200410039112A CN1251989C CN 1251989 C CN1251989 C CN 1251989C CN 200410039112 CN200410039112 CN 200410039112 CN 200410039112 A CN200410039112 A CN 200410039112A CN 1251989 C CN1251989 C CN 1251989C
- Authority
- CN
- China
- Prior art keywords
- slurry
- ceramic slurry
- concentration
- initiator
- bubble
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The present invention discloses a novel method for gel-casting ceramic slurry to eliminate air bubbles, which belongs to a forming technology of ceramics. In the method, a polymerization inhibitor is added to ceramic slurry to protect the ceramic slurry against solidification when the ceramic slurry is vacuumized. An initiator, a catalyst and a polymerization inhibitor which is compounded from phenothiazine and pyrocatechol are added to the ceramic slurry, the mixture is evenly stirred, air bubbles are eliminated by vacuumizing the mixture to eliminate air for 10 to 15 minutes, ceramic slurry with good mobility and nearly no air bubbles is obtained, and the obtained ceramic slurry can be directly used for casting. The amount of the polymerization inhibitor can prolong the required time for the solidification of the ceramic slurry, thereby ensuring enough operating time for vacuumizing the ceramic slurry; meanwhile, the adequate addition amount of the polymerization inhibitor ensures the easy solidification of the ceramic slurry in the following processes.
Description
Technical field
The invention belongs to the forming process of ceramics technology, particularly utilize to add the method for stopper to guarantee that slurry can a kind of gel casting forming ceramic size of solidified vacuum stripping bubble when vacuumizing.
Background technology
The preparation technology of high performance ceramic material and parts is prerequisites of stupalith development and application.And moulding technology plays a part to form a connecting link in the preparation process of whole stupalith, is reliability, yield rate and the repeatable key that guarantees stupalith and parts, and is directly related with industrialization and large-scale production.Enter after the nineties, round improving the ceramic body homogeneity and solving the stupalith reliability problems, colloidal state consolidation in-situ forming technology is arisen at the historic moment and is become the focus of research, gel casting forming (Gelcasting), temperature-induced flocculation moulding (Temperature Induced Floculation), directly solidifies casting new forming methods such as (DirectCoagulation Casting) and occurs in succession.
Wherein, gel casting forming is a kind of important ceramic in-situ consolidation colloidal forming technology that is subjected to extensive concern in recent years.It has the complicated ceramic component of near-net-shape, good even green body, high blank strength, excellent sintering character, and advantages such as organic content is low in simple to operate, the base substrate, has been widely used in the moulding of various ceramic systems.Its principle is to utilize the crosslinking reaction of organic monomer, the ceramic powder particle in-situ is set in the macromolecular elastomer equably, thus the goods of preparation definite shape.
If contain bubble in the slurry, bubble will be retained in base substrate inside behind the slurry curing so, influences the quality of final finished, therefore must be before injection molding through removing the step of bubble, and the most frequently used method is exactly vacuum stripping.But in actual mechanical process, there is a problem.In the gel casting forming, slurry still can keep good flowability for some time after adding initiator and catalyzer.This mainly is to be caused by the oxygen that is dissolved in the slurry, and the oxygen that is dissolved in the slurry can play significant inhibition, forms the very low peroxy radical of reactive behavior after it and the living radical addition, thereby makes polymerization stop.Just begin to solidify up to the oxygen depletion disposed slurry that finishes.Because must stir when in slurry, adding catalyzer, initiator, can in slurry, introduce new bubble and stir, after adding catalyzer, initiator so vacuum stripping is normally carried out.Water content only is about 20wt% in the ceramic size, is dissolved in the free radical reaction that oxygen wherein will produce with decomposition of initiator on the one hand, the volatilization rapidly owing to vacuumize again on the other hand.If so the time that vacuumizes is longer, oxygen is easy to all consume, and makes slurry just solidify in advance in vacuum degassed process; If the time that vacuumizes is too short, can make that again the bubble in the slurry does not eliminate.And, contain the reductibility ion of trace in some ceramic powder, these ions can with initiator generation redox reaction, make the easier curing of slurry, the operating time of Yun Xuing is just shorter like this.Address this problem, add the resistance polymers matter of non-volatility in the past in the ceramic size, to guarantee that slurry can not solidify after oxygen depletion finishes yet.Key wherein just is to seek suitable resistance polymers matter, and existing higher resistance gathers efficient, does not influence the curing of injection molding disposed slurry again.
Summary of the invention
The objective of the invention is to propose a kind of method of gel casting forming ceramic size vacuum stripping bubble, it is characterized in that: the method for described gel casting forming ceramic size vacuum stripping bubble, carry out as follows successively:
1). with acrylamide and N, N '-methylene-bisacrylamide is with 150: 1-5: 1 weight proportion is dissolved in and is made into premixed liquid in the deionized water, acrylamide concentration is 6-35wt%, N, N '-methylene-bisacrylamide concentration is 0.1-1wt%, adds the ceramic size that ceramic powder and dispersion agent ball milling obtain 30-60wt%;
2) under agitation condition, in ceramic size, add initiator, adding back initiator concentration in slurry is 0.2-10mmol/L, with the catalyzer that adds 2-3mmol, add stopper again, after continuation is stirred and was waited to be uniformly dispersed in 1-10 minute, vacuumize and removed bubble in degasification 10-15 minute, obtain good fluidity and bubble-free substantially slurry, can be directly used in injection molding.
Described stopper is to be that the thiodiphenylamine of 5～50mmol/L and pyrocatechol that concentration is 5～500mmol/L were dissolved in the ethanol and are made in 2: 1 in molar ratio～1: 10 with concentration.
Described stopper makes thiodiphenylamine and the pyrocatechol concentration in slurry be respectively 0.01mmol/L～0.2mmol/L and 0.1mmol/L～3.0mmol/L after adding slurry.
Described initiator can be used ammonium persulphate, Potassium Persulphate or hydrogen peroxide
Described catalyzer is N, N, N ', N '-Tetramethyl Ethylene Diamine.
The invention has the beneficial effects as follows and added stopper again after in slurry, adding initiator, catalyzer, utilize the stopper that adds to prolong the required time of slurry curing, thereby guarantee enough operating times of vacuum stripping, guaranteed the smooth curing of slurry in the subsequent technique again.
Embodiment
The present invention proposes a kind of method of gel casting forming ceramic size vacuum stripping bubble, in slurry, add initiator, catalyzer and with thiodiphenylamine and the compound use of pyrocatechol as stopper, can guarantee that slurry can not solidify, and carries out successively as follows when vacuumizing degasification:
The stopper that emphasis utilization of the present invention adds prolongs the required time of slurry curing, thereby guarantees that vacuum stripping has enough operating times, and suitable add-on has guaranteed the smooth curing of slurry in the subsequent technique again simultaneously.At first press the gel casting forming method, with concentration be 6-35wt% the organic monomer acrylamide monomer and and concentration be that the linking agent methylene-bisacrylamide of 0.1-1wt% is dissolved in and is made into premixed liquid in the deionized water, adding ceramic powder and dispersion agent are made into high solid loading in premixed liquid again, and viscosity is less than the ceramic size of 1Pas.The ammonium persulphate that under agitation condition, adds 0.2-10mmol/L in the slurry, Potassium Persulphate or hydrogen peroxide are made initiator and catalyst n, N, N ', N '-Tetramethyl Ethylene Diamine 2-3mmol, adding concentration is that thiodiphenylamine and the concentration of 5～50mmol/L is the pyrocatechol of 5～500mmol/L again, be dissolved in 2: 1 in molar ratio～1: 10 and be made into stopper in the ethanol, after adding slurry, make thiodiphenylamine and the pyrocatechol concentration in slurry be respectively 0.01mmol/L～0.2mmol/L and 0.1mmol/L～3.0mmol/L, then slurry is carried out vacuum stripping, obtain good fluidity and bubble-free substantially slurry.
For embodiment the present invention is further specified again below.
Embodiment 1
With commercially available TiO
2Be raw material, be mixed with the slurry of 50vol%.Get the 0.125g thiodiphenylamine, the 0.345g pyrocatechol is dissolved in 100ml ethanol and is made into stopper.Get the 100ml slurry, under agitation condition, add 0.14mmol ammonium persulphate, 2mmol N, N, N ', N '-Tetramethyl Ethylene Diamine.Vacuumizing 10 minutes disposed slurries of degasification under 30 ℃ of conditions of envrionment temperature has cured.Get the 100ml slurry again, under agitation condition, add 0.14mmol ammonium persulphate, 2mmol N, N, N ', N '-Tetramethyl Ethylene Diamine and 100 μ l stoppers.Vacuumize degasification after 10 minutes under 30 ℃ of conditions of envrionment temperature, slurry fluidity is good and the injection molding rear curing time is constant substantially.
Embodiment 2
With commercially available Al
2O
3Be raw material, be mixed with the slurry of 55vol%.Get the 0.125g thiodiphenylamine, the 0.345g pyrocatechol is dissolved in 100ml ethanol and is made into stopper.Get the 100ml slurry, under agitation condition, add 0.25mmol Potassium Persulphate, 3mmol N, N, N ', N '-Tetramethyl Ethylene Diamine.Vacuumizing 15 minutes disposed slurries of degasification under 30 ℃ of conditions of envrionment temperature has cured.Get the 100ml slurry again, under agitation condition, add 0.25mmol Potassium Persulphate, 3mmol N, N, N ', N '-Tetramethyl Ethylene Diamine and 200 μ l stoppers.Vacuumize degasification after 10 minutes under 30 ℃ of conditions of envrionment temperature, slurry fluidity is good and the injection molding rear curing time is constant substantially.
Embodiment 3
With commercially available Al
2O
3Be raw material, be mixed with the slurry of 55vol%.Get the 0.125g thiodiphenylamine, the 0.345g pyrocatechol is dissolved in 100ml ethanol and is made into stopper.Get the 100ml slurry, under agitation condition, add 0.25mmol hydrogen peroxide, 3mmol N, N, N ', N '-Tetramethyl Ethylene Diamine.Vacuumizing 15 minutes disposed slurries of degasification under 30 ℃ of conditions of envrionment temperature has cured.Get the 100ml slurry again, under agitation condition, add 0.25mmol hydrogen peroxide, 3mmol N, N, N ', N '-Tetramethyl Ethylene Diamine and 200 μ l stoppers.Vacuumize degasification after 10 minutes under 30 ℃ of conditions of envrionment temperature, slurry fluidity is good and the injection molding rear curing time is constant substantially.
Claims (3)
1. the method for gel casting forming ceramic size vacuum stripping bubble, it is characterized in that: in slurry, add and add again behind initiator, the catalyzer with thiodiphenylamine and the compound use of pyrocatechol as stopper, to guarantee that slurry can not solidify when vacuumizing degasification, carry out as follows successively:
1) with acrylamide and N, N '-methylene-bisacrylamide is with 150: 1-5: 1 weight proportion is dissolved in and is made into premixed liquid in the deionized water, wherein acrylamide concentration is 6-35wt%, N, N '-methylene-bisacrylamide concentration is 0.1-1wt%, adds the ceramic size that the ceramic powder ball milling obtains 30-60wt%;
2) under agitation condition, add the catalyzer of initiator and 2-3mmol in the ceramic size, adding back initiator concentration in slurry is 0.2-10mmol/L, add stopper again, after continuation is stirred and was waited to be uniformly dispersed in 1-10 minute, vacuumize and removed bubble in degasification 10-15 minute, obtain good fluidity and bubble-free slurry, be directly used in injection molding; Wherein stopper is to be that the thiodiphenylamine of 5～50mmol/L and pyrocatechol that concentration is 5～500mmol/L were dissolved in the ethanol and are made in 2: 1 in molar ratio～1: 10 with concentration, after stopper adds slurry, continue to stir and disperseed in 1-10 minute, make thiodiphenylamine and the pyrocatechol concentration in slurry be respectively 0.01mmol/L～0.2mmol/L and 0.1mmol/L～3.0mmol/L.
2. according to the method for the described gel casting forming ceramic size of claim 1 vacuum stripping bubble, it is characterized in that: described initiator is selected ammonium persulphate, Potassium Persulphate or hydrogen peroxide for use.
3. according to the method for the described gel casting forming ceramic size of claim 1 vacuum stripping bubble, it is characterized in that: described catalyzer is N, N, N ', N '-Tetramethyl Ethylene Diamine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410039112 CN1251989C (en) | 2004-02-06 | 2004-02-06 | Novel vacuum degassing method for gelcasting ceramic slurry |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410039112 CN1251989C (en) | 2004-02-06 | 2004-02-06 | Novel vacuum degassing method for gelcasting ceramic slurry |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1557769A CN1557769A (en) | 2004-12-29 |
| CN1251989C true CN1251989C (en) | 2006-04-19 |
Family
ID=34352270
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410039112 Expired - Fee Related CN1251989C (en) | 2004-02-06 | 2004-02-06 | Novel vacuum degassing method for gelcasting ceramic slurry |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1251989C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102430425A (en) * | 2011-09-01 | 2012-05-02 | 神华集团有限责任公司 | Pre-treatment method for molecular sieve catalyst forming, forming method and catalyst product |
| CN103496999B (en) * | 2013-09-18 | 2015-10-28 | 清华大学 | A kind of method adopting ceramic hollow ball to prepare porous ceramics |
| CN112456978A (en) * | 2020-11-25 | 2021-03-09 | 上海三思电子工程有限公司 | Ceramic slurry and preparation method and application thereof |
| CN114988880B (en) * | 2022-07-15 | 2023-03-31 | 河南淅川平煤三责精密陶瓷有限公司 | Preparation method for preparing silicon carbide ceramic through gel injection molding and pressureless sintering |
-
2004
- 2004-02-06 CN CN 200410039112 patent/CN1251989C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1557769A (en) | 2004-12-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107540883B (en) | Preparation method of carboxymethyl chitosan/graphene oxide/poly (N-isopropylacrylamide) nano composite hydrogel | |
| CN109400779B (en) | Preparation method of phenolic hydroxyl self-polymerization hydrogel | |
| CN109836596A (en) | The high-intensitive preparation method with the amylopectin composite hydrogel of high adherency of strong hydrogen bonding effect | |
| CN1778760A (en) | Gel molding-injection base from high-strength ceramic composite materials and shaping method thereof | |
| CN1251989C (en) | Novel vacuum degassing method for gelcasting ceramic slurry | |
| CN112341637A (en) | Composition for polymer gel, gel prepared from composition and application of gel | |
| CN103373848A (en) | Preparation and curing process of ZrO2 gel-casting slurry | |
| CN110642964A (en) | Epoxy functional rubber crosslinked elastomer capable of being repeatedly processed and preparation method thereof | |
| CN103356391B (en) | Dual curing crown nuclear resin for dentistry and preparation method thereof | |
| CN101597436A (en) | Silicon powder surface treating process for modifying and composition epoxy resin and preparation method thereof | |
| CN1872458A (en) | Injection moulding method for Ti6A14V alloy gel | |
| US9630854B2 (en) | Silicon carbide powder | |
| CN101348376B (en) | Double-component monomer system for ceramic material gel pouring moulding and use method thereof | |
| CN105199178A (en) | Three-dimensional printing photosensitive resin material containing modified butadiene rubber and preparation method | |
| CN1513811A (en) | Cermic Sizing material fast and controllable solidfying colloied state shaping method and device | |
| JP2008504417A (en) | Polyvinyl acetate-solid resin functionalized with acid groups | |
| CN101224983A (en) | Gel casting method for pre-reduced hard magnetic ferrite ceramic parts | |
| CN110577804B (en) | Environment-friendly acrylate adhesive with low TVOC (total volatile organic compound) | |
| CN101058511A (en) | Molding process of water system aluminum oxide containing ceramic slurry gel | |
| US20160137512A1 (en) | Silicon carbide powder | |
| CN1718661A (en) | Modified urea formaldehyde binding agent and its preparation method | |
| CN1227085C (en) | Injection coagution forming technology for metal powder | |
| CN114455946A (en) | Zirconia ceramic powder for photocuring 3D printing and preparation method thereof | |
| CN111925618A (en) | Inorganic composite material doped resin material with enhanced mechanical property | |
| CN108372293A (en) | A kind of method of metal powder gel injection molding catalysis degumming |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20060419 Termination date: 20100206 |